石油炼制与化工 ›› 2012, Vol. 43 ›› Issue (10): 16-21.

• 催化剂 • 上一篇    下一篇

硫化压力对CoMo/Al2O3加氢脱硫催化剂活性的影响

杜辉1,2,郭蓉2,3,杨成敏2,苏爱平1,2   

  1. 1. 辽宁石油化工大学石油化工学院
      2. 中国石化抚顺石油化工研究院
      3. 华东理工大学化工学院
  • 收稿日期:2012-01-09 修回日期:2012-02-09 出版日期:2012-10-12 发布日期:2012-09-26
  • 通讯作者: 郭蓉 E-mail:guorong.fshy@sinopec.com

EFFECT OF SULFIDATION PRESSURE ON THE ACTIVITY OF CoMo/Al2O3 HYDRODESULFURIZATION CATALYST

  • Received:2012-01-09 Revised:2012-02-09 Online:2012-10-12 Published:2012-09-26

摘要: 采用固定床微反装置对一工业CoMo/Al2O3催化剂在不同压力下进行硫化,并对硫化态催化剂进行了加氢脱硫活性评价;借助高分辨透射电镜(TEM)、X射线光电子能谱(XPS)等手段对硫化态催化剂进行了表征。TEM结果表明,随着硫化压力的升高,MoS2片晶的堆积层数和长度均有所增加,有利于减弱活性金属与载体间的强相互作用。XPS结果表明,随着硫化压力的升高,催化剂的硫含量以及硫化程度均逐渐增大,有利于催化剂活性的提高。此外,4.0 MPa压力下反应18 h后催化剂的XPS表征结果表明,由于反应压力比硫化压力有所提高,对催化剂存在补充硫化的作用。催化剂活性评价结果证实了TEM与XPS表征结果,在硫化压力4.0 MPa、反应温度360 ℃时催化剂的加氢脱硫活性最高,脱硫率达到99.5%。

Abstract: A commercial CoMo/Al2O3 hydrodesulfurization (HDS) catalyst was sulfurized in a fixed-bed micro-reactor under various pressures. The sulfurized catalyst samples were characterized by high-resolution transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS), as well as HDS activity evaluation. The TEM results show that the number of stacking layers and the length of MoS2 nano-particles increase with the sulfidation pressure, which is helpful to weaken the interaction of metal-support. The XPS results show that the sulfur content and the sulfidation degree of the sulfurized catalyst increase with the sulfidation pressure, which benefits the improvement of catalyst activity. Moreover, supplemental sulfidation may happen during the HDS reaction due to reaction pressure is higher than sulfidation pressure sometimes, and it is shown from the XPS results of catalysts reacted under 4.0 MPa for 18 h. The evaluation data of catalyst performance agree well with the characterization results, under a reaction temperature of 360 ℃ and a reaction pressure of 4.0 MPa, catalysts exhibit high activities, the maximum HDS rate reaches 99.5%.